Herbicidal aryl triazolinones

ABSTRACT

Herbicidal compounds of the formula   &lt;IMAGE&gt;   in which, for example, X is Br, Cl or F; Y is Cl or Br, R2 is CHF2, R3 is CH3 R is lower alkyl and R1 is H,Na, lower alkyl or -SO2R.

This application is a continuation-in-part, of application Ser. No.811,615, filed Dec. 20, 1985, now abandoned.

The invention described in this application pertains to weed control inagriculture, horticulture, and other fields where there is a desire tocontrol unwanted plant growth. More specifically, the presentapplication describes certain herbicidal aryl triazolinones,compositions of them, methods of preparing them, and methods forpreventing or destroying undesired plant growth by preemergence orpostemergence application of the herbicidal compositions to the locuswhere control is desired. The present compounds may be used toeffectively control a variety of both grassy and broadleaf plantspecies. The present invention is particularly useful in agriculture; anumber of the compounds described herein show a selectivity favorable tocertain crops (e.g. soybeans on preemergence treatment) at applicationlevels which inhibit the growth of or destroy a variety of weeds.

One aspect of this invention relates to herbicidal compounds of thegeneral formula ##STR2## wherein X is bromine, chlorine, or fluorine oralkyl (e.g. CH₃) or haloalkyl (e.g. CF₃);

Y is bromine, chlorine, fluorine, methyl, haloalkyl (e.g. FCH₂ or CF₃),nitro, a radical of the formula R⁸ OCH₂ --, R⁸ SCH₂ --, R⁸ SOCH₂ --or R⁸SO₂ CH₂ -- where R⁸ is C₁ -C₃ alkyl, C₂ -C₅ alkenyl, or C₃ -C₅ alkynyl(e.g., CH₃ OCH₂ --, CH₃ SCH₂ --, CH₂ ═CHCH₂ OCH₂ --CH₂ ═CHCH₂ SCH₂ --,CH.tbd.CCH₂ OCH₂ --, or CH.tbd.C--CH₂ SCH₂); R⁸ may also be phenyl (orphenyl substituted with e.g., halogen, alkyl, haloalkyl),

R³ may be halogen (e.g. chlorine), alkyl (e.g. of 1 to 5 carbon atoms),haloalkyl (e.g. of 1 to 5 carbon atoms such as difluoromethyl),alkoxyalkyl (e.g. of 2 to 6 carbon atoms such as methoxymethyl),cyanoalkyl (e.g. of 2 to 6 carbon atoms such as cyanomethyl), arylalkylsuch as benzyl, alkylthio (e.g. of 1 to 3 carbon atoms such asmethylthio) or the corresponding alkylsulfinyl or alkylsulfonyl, oralkylthioalkyl (e.g., of 1 to 3 carbon atoms independently with respectto each alkyl, such as methylthiomethyl) or the correspondingalkylsulfinylalkyl or alkylsulfonylalkyl;

R² may be alkyl (e.g. of 1 to 5 carbon atoms), lower alkoxy (e.g.methoxy), haloalkyl (e.g. of 1 to 5 carbon atoms, such as CHF₂ or CH₂CH₂ CH₂ F), alkenyl of 2 to 5 carbon atoms (e.g. allyl), alkynyl of 3 to5 carbon atoms (e.g. propargyl), cyanoalkyl (e.g. CH₂ CN or CH₂ CH₂ CN),thiocyanoalkyl (e.g. CH₂ SCN) or a group of the formula --alkylene--Y¹--R⁵ in which said alkylene group (e.g. --CH₂ --) has 1 to 5 carbonatoms, Y¹ being oxygen or S(O)_(r) in which r is 0 to 2, and R⁵ beingalkyl (e.g. of 1 to 5 carbon atoms such as methyl), alkenyl of 2 to 5carbon atoms (e.g. allyl) or alkynyl of 3 to 5 carbon atoms (such aspropargyl);

R may be alkyl (such as straight chain or branched chain lower alkyl,e.g. methyl, ethyl, propyl), haloalkyl (such as CF₃ or CHF₂),dialkylamino, carboxymethyl, hydroxy or aryl (such as phenyl, optionallysubstituted with one or more of: halogen such as Cl, Br or F; alkyl suchas lower alkyl, e.g. methyl; alkoxy such as lower alkoxy, e.g. methoxy;cyano; cyanomethyl; nitro; amino; arylamino such as phenylamino; mono-and dialkylamino such as methylamino or dimethylamino; carboxyl;alkoxycarbonyl such as --COOC₂ H₅ ; alkoxyalkyl such as alkoxymethyl of2 to 4 carbon atoms; alkoxycarbonylalkyl such as --CH₂ COOC₂ H₅ ;benzyl; or hydroxy).

R¹ may be hydrogen, alkyl (e.g. straight or branched chain lower alkylsuch as methyl, ethyl, propyl, isopropyl or butyl), benzyl, haloalkyl(e.g. CHF₂ or CH₂ CH₂ CH₂ F), alkoxy (e.g. methoxy), SO₂ R, alkynyl(such as propargyl), alkenyl (such as allyl), a group of the formula--alkylene--SO₂ R (in which, for example, said alkylene group (e.g.--CH₂ --) has 1 to 4 carbon atoms, alkoxymethyl (such as methoxymethyl,cyanomethyl, carboxymethyl (including salts thereof) oralkoxycarboynlmethyl (e.g. or ethoxycarbonylmethyl).

R and R¹ together may be a divalent radical such as alkylene (e.g. of 1to 10 carbon atoms such as methylene or 1,3-propylene).

R¹ may also be a salt-forming group such as a metal (e.g. Na, K or Ca)or ammonium (e.g. NH₄ or lower alkyl-substituted ammonium or sulfoniumor sulfoxonium (such as salts of bases of the formula R"₃ S(O)_(n) whereR" is, for instance, lower alkyl (e.g. C₁ -C₃ alkyl and n is zero orone, e.g. the trimethylsulfoxonium salt).

In each aspect of the invention, it is often preferable that any alkyl,alkenyl, alkynyl or alkylene radical have less than 6 carbon atoms.

Representative compounds according to the invention are shown in Table 1below.

The compounds of this invention are preferably those whose MethoxyAnalog or Propargyloxy Analog is a herbicide. The term "Methoxy Analog"is used here to designate a compound which is otherwise identical exceptthat it has a methoxy group instead of the ##STR3## group of saidcompound. The term "Propargyloxy Analog" is similarly used here for acompound which is otherwise identical except that it has a propargyloxygroup instead of the ##STR4## group of said compound.

The compounds of this invention preferably have Methoxy Analogs andPropargyloxy Analogs of marked herbicidal properties. For instance saidAnalogs of the preferred compounds show at least 50% kill of at leastone of the following species of plants when applied under at least oneof the following modes at the rate of 0.5 kg/ha, and more preferablyshow such kill of at least 50% when applied to the rate of 0.1 kg/ha:Species: velvetleaf (Abutilon theophrasti), green foxtail (Setariaviridis); Modes: pre-emergent, post-emergent. Testing for suchherbicidal activity may be carried out in the manner described below(under the heading "Herbicidal Activity").

The compounds of this invention may be prepared by the use of stepsgenerally described in the literature or by methods analogous or similarthereto and within the skill of the art. In the Examples below anarylamine is treated to form the corresponding aryl hydrazine whosehydrazine portion is then modified to form a triazolinone ring.Thereafter the benzene ring of the intermediate is nitrated, the nitrogroup is reduced to form an amino group, which is then treated with RSO₂Cl or (RSO₂)₂ O to convert it to an --N (R')SO₂ R group (e.g. by using aweak base such as pyridine, as in Example 19 below, or NaHCO₃) or to an--N(SO₂ R)₂ group (as in Examples 2, 5, 9, 12, 14 or 17). The compoundhaving the --N(SO₂ R)₂ group may then be treated (as with a base such asNaOH) to form the corresponding --NR¹ SO₂ R group, where R¹ is asalt-forming group (e.g. Na); this may then be treated with an acid toform the corresponding (acidic) --NHSO₂ R group. Subsequent alkylation(as by treatment with the appropriate alkyl halide as in Example 7)forms the corresponding ##STR5## group R¹ substituents other than alkylmay be introduced similarly in known manner. When the reaction sequenceinvolves RSO₂ Cl treatment of an intermediate having hydrogen on the4-nitrogen of the triazolinone ring, that hydrogen may also be replaced,during such treatment, by RSO₂ --to form an intermediate (such ascompound 36 in table 1 below, which has 3 RSO₂ --groups) from which theRSO₂ -- group on said 4-nitrogen may be removed readily by the treatmentwith the base, after which the appropriate R² group may be substitutedon said 4-nitrogen.

In the Examples the modification of the hydrazine group to form atriazolinone ring is effected by reaction with pyruvic acid (forming thehydrazone) and then with a phosphoryl azide. Other techniques for thisinclude treating the substituted phenylhydrazine with any of thefollowing four types of reagents:

(a) an inner salt of a 3-(1-iminoalkylmercapto)-1-propanesulfonic acid(which may be prepared according to Reid and Schmidt, Ann. Chem. 676,114 (1964) from 1,3-propanesultone and a thioamide), to form anamidrazone followed by reaction with a source of phosgene, as by thefollowing reaction sequence (which is also illustrated in Example 15below), ##STR6## in which "Ar" is aromatic as described below.

(b) An imidate ester of the formula ##STR7## to form the correspondingamidrazone (as described, for instance, in the article by Neilson et al"The Chemistry of Amidrazones": Chem. Rev. 70, 151 (1970) at page 156),followed by reaction with a source of phosgene, as in (a) above, R^(c)and R^(d) being alkyl or other suitable radical.

(c) A compound of the formula ##STR8## (where R^(a) and R^(b) are loweralkyl) in the presence of a base according to the following sequence:##STR9## in which R¹ is defined above, e.g. methyl;

(d) A haloalkylnitrile (e.g. a fluoroalkyl, fluorochloroalkyl orfluorobromoalkyl nitrile such as ClCF₂ CN, followed by reaction with asource of phosgene, so that the reaction may proceed along the followinglines, for instance to form the aryl 3-haloalkyl triazoline, thus:##STR10##

In Examples 1, 8 and 13 below two halogen substituents are present onthe "Ar" portion of the molecule before the triazoline ring is formed;that is, the Ar portion of the aryl hydrazine has halo substituents atits 2 and 4 positions. Instead, in each of the processes illustratedabove (and in the process of those Examples 1, 8 and 13) one or both ofthe halogens may be placed on Ar after the triazoline ring is formed.Thus the Ar group of the arylamine (and of the corresponding hydrazineformed therefrom) may be phenyl or monohalophenyl (e.g. 2-fluorophenyl)or nitrophenyl (e.g. 3-nitrophenyl) or monohalonitrophenyl (e.g.2-fluoro-5-nitrophenyl) and the aryl triazoline formed therefrom maythen be treated to (a) alkylate the nitrogen at the 4-position of thetriazoline ring (in known manner, e.g. with an alkyl or fluoroalkylhalide, such as with ClCHF₂ , at a temperature of, say, 50° to 150° C.)to add the preferred-CHF₂ substituent) and (b) to introduce additionalsubstituents onto the aromatic ring, as by halogenation with chlorine orbromine (e.g. by reacting with Cl₂, Br₂ or SO₂ Cl.sub. 2 at atemperature of, say, 20° to 150° C.). For instance the alkylation of thenitrogen at the 4-position may be effected first, after which the nitrogroup (if present) may be reduced to an amino group in conventionalmanner, the amino group may be converted to the organic sulfonylaminogroup (e.g. in the manner shown in the Examples using, for instance, atemperature below 60° C. such as -10° to 50° C. in the presence of asuitable base and an inert solvent), after which the compound may behalogenated as indicated above to place the halogen substitutent orsubstituents on its benzene ring. For instance, for making one preferredclass of compounds of the invention in which the benzene ring has a2-fluoro substituent, the starting material may be2-fluoro-5-nitrophenylhydrazine, which may be treated as described aboveto produce successively a series of intermediates such as:

1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-methyl1,2,4-tirazol-5(1H)-one,then

1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,then

1-(2-fluoro-5-aminophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,then

the corresponding compound having an ##STR11## group at the 5-positionof the benezene ring such as1-[2-fluoro-5-(N-ethylsulfonyl)aminophenyl]-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,

followed by halogenation to place, for instance, a chloro or bromosubstituent at the 4-position of the benzene ring.

Instead of alkylating at the 4-position of the ring triazoline at anearly stage, e.g. prior to altering the nitro group, this alkylationstep may be delayed until after the above-described halogenation of thebenezene ring.

Another series of intermediates comprises:

1-(5-nitrophenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, then

1-(5-nitorphenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,then

1-(5-aminophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,then

the corresponding compound having an ##STR12## group at a meta-positionon the benzene ring such as1-[5-(N-ethylsulfonyl)aminophenyl]-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,

followed by halogenation to place, for instance, two chloro (or bromo)substituents at the 2- and 4-positions of the benzene ring.

Variations in the sequence in which the reactions are carried out willproduce other intermediates such as:

1-(2-chloro-5-nitrophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,which may be converted to the corresponding 2-fluoro-5-nitrophenylcompound by appropriate treatment with KF to replace the 2-chlorosubstituent by a 2-fluoro substituent;

also, 1-(2-fluorophenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,which may be converted to

1-(2-fluorophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-onewhich may then be chlorinated, as by appropriate treatment with SO₂ Cl₂,to the corresponding 2-fluoro-4-chlorophenyl compound.

Another sequence involves formation of:

2-fluoro-4-nitrophenylhydrazine, then

1-(2-fluoro-4-nitrophenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,then

1-(2-fluoro-4-nitrophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,then

1-(2-fluoro-4-aminophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one,followed by treatment to replace the amino group by a chlorine (as bytreatment with NaNO₂ /HCl and then CuCl).

Similarly, when the reagent(s) used to react with the aryl hydrazine aresuch as to produce a triazolinone having a haloalkyl (e.g. CHF₂) groupinstead of an alkyl group on the carbon at the 3-position of theheterocyclic ring, the series of intermediates may include, successively(from 2-fluoro-5-nitrophenylamine, and then its hydrazine) suchcompounds as:

1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5(1H)-one,then

1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one, then

1-(2-fluoro-5-aminophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one, then

the corresponding compound having an ##STR13## group at the 5-positionof the benzene ring such as1-[2-fluoro-5-(N-ethylsulfonyl)aminophenyl]-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one,

followed by halogenation to place, for instance, a chloro or bromosubstituent at the 4-position of the benzene ring.

Another series of intermediates, fom 5-nitrophenylamine includes:

1-(5-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5(1H)-one,then 1-(5-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one, then

1-(5-aminophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one, then

the corresponding compound having an ##STR14## group at a meta-positionon the benzene ring such as1-[5-(N-ethylsulfonyl)aminophenyl]-4,5-dihydro-4-methyl ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one,

followed by halogenation to place, for instance, two chloro (or bromo)substituents at the 2- and 4-positions of the benzene ring.

Variations in the sequence in which the reactions are carried out willproduce other intermediates such as:

1-(2-chloro-5-nitrophenyl)-4,5-dihydro-4-(methyl ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one, which may beconverted to the corresponding 2-fluoro-5-nitrophenyl compound byappropriate treatment with KF to replace the 2-chloro substituent by a2-fluoro substituent;

also,1-(2-fluorophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5(1H)-one,which may be converted to

1-(2-fluorophenyl)-4,5-dihydro-4-methyl(ordifluoromethyl)-3-methyl-1,2,4-triazol-5(1H)-one which may then bechlorinated, as by appropriate treatment with SO₂ Cl₂ to thecorresponding 2-fluoro-4-chlorophenyl compound.

Another sequence involves formation of:

2-fluoro-4-nitrophenylhydrazine, then

1-(2-fluoro-4-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5(1H)-one,then

1-(2-fluoro-4-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-dibluoromethyl-1,2,4-triazol-5(1H)-one, then

1-(2-fluoro-4-aminophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one, followed bytreatment to replace the amino group by a chlorine (as by treatment withNaNo₂ /HCl and the CuCl).

Alternatively, one may start with 4-fluoronitrobenzene and, by a seriesof reactions (e.g. by reducing the NO₂ group to an amino group and thennitrating to form 3-nitro-4-fluoroaniline, followed by treatment withthe alkylsulfonyl halide), form2-fluoro-5-bis(N-ethylsulfonylamino)nitrobenzene, which is then reducedto form 2-fluoro-5-bis(N-ethylsulfonyl)amino aniline and then convertedto the corresponding1-[2-fluoro-5-bis(N-ethylsulfonyl)amino-phenyl]-3-methyl-Δ²-1,2,4-triazolin-5-one, which may then be treated to substitute an R³group on the triazolinone ring.

From 2-fluoro-5-nitroaniline one may (as illustrated in Example 20)acetylate the NH₂ to protect it; then reduce the nitro group to form anamino group; chlorinate and treat with alkylsulfonyl chloride in anyorder (to form, e.g.,2-fluoro-4-chloro-5-(ethylsulfonylamino)acetanilide); then hydrolyze offthe acetyl group to form2-fluoro-4-chloro-5-(ethylsulfonylamino)aniline, whose free NH₂ groupmay then be converted (e.g. as discussed above) to a triazolinone ring.

Similarly, starting with 2-fluoro-4-chloro-5-nitroaniline one mayacetylate to form 2-fluoro-4-chloro-5-nitroacetanilide (m.p. 138°-140°C.); reduce to form 2-fluoro-4-chloro-5-aminoacetanilide (m.p. 117°-120°C., dec.) and then alkylsulfonate to form, e.g.2-fluoro-4-chloro-5-bis(N-ethylsulfonylamino) acetanilide (m.p.217°-219° C.) and/or2-fluoro-4-chloro-5-(N-ethyl-sulfonylamino)acetanilide, which may betreated to hydrolyze off the acetyl group and then converted to atriazolinone as discussed above.

The following Examples illustrate the preparation of the compounds ofthis invention. In those Examples the hetercyclic ring is described as:Δ² -1,2,4-triazolin-5-one; that is a synonym for:dihydro-1,2,4-triazol-5(1H)-one.

EXAMPLE 1 SYNTHESIS OF1-(5-AMINO-4-CHLORO-2-FLUOROPHENYL)-3-METHYL-4-DIFLUOROMETHYL-Δ.sup.2-1,2,4-TRIAZOLIN-5-ONE AS AN INTERMEDIATE Step A Synthesis of2-Fluoroacetanilide as an Intermediate

To a stirred solution of 100 g (0.9 mole) of 2-fluoroaniline in 200 mlof water was added 105 ml (1.1 moles) of acetic achydride. Uponcompletion of addition the reaction mixture was filtered to collect asolid. The solid was dried to yield 105 g of 2-fluoroacetanilide; m.p.74°-76° C. The reaction was repeated several times.

Step B Synthesis of 4-Chloro-2-fluoroacetanilide as an Intermediate

To a stirred solution of 180.0 g (1.17 moles) of 2-fluoroacetanilide in210 ml of p-dioxane was slowly added dropwise 173.4 g (9.29 moles) ofsulfuryl chloride. Upon completion of addition the reaction mixturestirred at ambient temperature for 16 hours. A solid was collected byfiltration, washed with water, and dried to yield 155 g of4-chloro-2-fluoroacetanilide; m.p. 147°-148° C.

Step C Synthesis of 4-Chloro-2-fluoroaniline as an Intermediate

To a stirred solution of 155 g (0.83 mole) of4-chloro-2-fluoroacetanilide in 400 ml of ethanol was added dropwise asolution of 72.0 g (1.8 moles) of sodium hydroxide in 100 ml of water.Upon completion of addition the reaction mixture was heated under refluxfor three hours. The reaction mixture was cooled to ambient temperatureand extracted with diethyl ether. The combined extracts wereconcentrated under reduced pressure to a residual oil. The oil wasdistilled under reduced pressure to yield 81.0 g of4-chloro-2-fluoroaniline; b.p. 83-85/12 mm. The reaction was repeatedseveral times.

Step D Synthesis of Pyruvic Acid, 4-chloro-2-fluorophenylhydrazone as anIntermediate

Under a nitrogen atmosphere, a stirred solution of 20.0 g (0.137 mole)of 4-chloro-2-fluoroaniline in 162 ml of concentrated hydrochloric acidwas cooled to -9° C. and a solution of 9.5 g (0.137 mole) of sodiumnitrite in 50 ml of water was added dropwise at a rate to maintain thereaction mixture temperature at -9° C. The complete addition required 30minutes. The reaction mixture was stirred for an additional one hour at-9° C. to 0° C., then a solution of 68.1 g (0.30 mole) of stannouschloride in 68 ml of concentrated hydrochloric acid was added dropwiseat a rate to maintain the reaction mixture temperature at -9° C. to 0°C. The complete addition required 40 minutes. The reaction mixturestirred at -9° C. to 0° C. for an additional 30 minutes, then wasallowed to warm to ambient temperature where it stirred for two hours.Water, 110 ml, was added to the reaction mixture, and then a solution of12.2 g (0.137 mole) of pyruvic acid in 125 ml of water was addeddropwise during a five minute period. Upon completion of addition thereaction mixture stirred an additional 30 minutes then was filtered tocollect a solid. The solid was washed with water and dried to give 27.7g of pyruvic acid, 4-chloro-2-fluorohenylhydrazone; m.p. 162°-163° C.The reaction was repeated several times.

Step E Synthesis of 1-(4-chloro-2-fluoroophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

To a stirred suspension of 25.4 g (0.110 mole) of pyruvic acid,4-chloro-2-fluorophenylhydrazone in 200 ml of toluene was added 11.1 g(0.11 mole) of triethylamine. The reaction mixture became homogeneousand 30.3 g (0.11 mole) of diphenylphosphoryl azide was added. Uponcompletion of addition the reaction mixture was heated to reflux whereit stirred for two hours. The reaction mixture was cooled to ambienttemperature and extracted with 300 ml of aqueous 1N sodoum hydroxide.The extract was neutrailized with concentrated hydrochloric acid and asolid precipitate collected by filtration. The solid was washed withwater and dried to yield 21.1 g of1-(4-chloro-2-fluorophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one; m.p.189°-191° C. The reaction was repeated several times.

Step F Synthesis of1-(4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

A stirred solution of 27.4 g (0.12 mole) of1-(4-chloro-2-fluorophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one, 13.5 g(0.24 mole) of powdered potassium hydroxide, and 3.9 g (0.012 mole) oftetrabutylammonium bromide in 500 ml of tetrahydrofuran was cooled in anice bath and chlorodifluoromethane was bubbled into the reactionmixture. The ice bath was removed and chlorodifluoromethane continued tobubble into the reaction mixture until condensation of it was observedon a dry ice condenser attached to the reaction vessel. Upon completionof addition the reaction mixture stirred at ambient temperature for 16hours. An additional 6.7 g (0.12 mole) of powdered potassium hydroxidewas added to the reaction mixture and it was again saturated withchlorodifluoromethane. The reaction mixture was stirred for two hoursthen diluted with water. The mixture was extracted with diethyl etherand the combined extracts washed with water. The organic layer was driedwith sodium sulfate and filtered. The filtrate was concentrated underreduced pressure to a residue. The residue was dissolved in methylenechloride and passed through a pad of silica gel. The eluate wasconcentrated under reduced pressure to a residual solid. The solid wasrecrystallized from methylene chloride-heptane to yield 9.5 g of1-(4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-tetrazoline-5-one as a solid. The reaction was repeated severaltimes.

Step G Synthesis of1-(4-chloro-2-fluoro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one as an Intermediate

To a stirred solution of 6.1 g (0.022 mole) of1-(4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one in 9 ml of concentrated sulfuric acid was slowlyadded 1.96 ml of 70% nitric acid, while maintaining the reaction mixturetemperature at 25° C. Upon completion of addition the reaction mixturewas stirred at 25° C. for 30 minutes, then poured into ice water. Theresultant solid was collected by filtration. The solid was dissolved inmethylene chloride and passed through a pad of silica gel. The eluatewas subjected to column chromatography on silica gel. Elution wascompleted using 1:1-petroleum ether:methylene chloride. The appropriatefractions were combined and concentrated under reduced pressure to yield3.0 g of1-(4-chloro-2-fluoro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one; m.p. 102°-104° C. The reaction was repeatedseveral times.

Step H Synthesis of1-(4-amino-4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one as an Intermediate

To a stirred solution of 4.0 g (0.012 mole) of1-(4-chloro-2-fluoro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one in 50 ml of acetic acid and 20 ml of water wasadded portionwise 4.0 g (0.072 mole) of powdered iron at a rate tomaintain the reaction mixture temperature below 35° C. Upon completionof addition the reaction mixture stirred at 25°-30° C. for two hours.The reaction mixture was diluted with diethyl ether with stirring, thenwas filtered through diatomaceous earth. The stirred filtrate was madebasic with aqueous 10% sodium bicarbonate solution and solid potassiumcarbonate. The organic layer was separated, washed with three portionsof water, then dried with sodium sulfate. The mixture was filtered andthe filtrate concentrated under reduced pressure to a residue. Theresidue was purified by column chromatography on silica gel usingmethylene chloride:acetone as an eluent. The appropriate fractions werecombined and concentrated under reduced pressure to yield 3.1 g of1-(5-amino- 4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one; m.p. 128°-129° C. The nmr and the ir spectrawere consistent with the proposed structure. The reaction was repeatedseveral times.

EXAMPLE 2 SYNTHESIS OF1-[4-CHLORO-2-FLUORO-5-[BIS(N-METHYLSULFONYL)AMINO]PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 24)

A stirred solution of 1.0 g (0.003 mole) of1-(5-amino-4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one (prepared as in Example 1) and 0.76 g (0.008mole) of triethylamine in 20 ml of methylene chloride was cooled in anice/acetone bath and 0.83 g (0.007 mole) of methanesulfonyl chloride wasadded dropwise at a rate to maintain the reaction mixture temperaturebelow 0° C. The complete addition required five minutes. Upon completionof addition the reaction mixture was allowed to warm to ambienttemperature where it stirred for 16 hours. After this time the reactionmixture was concentrated under reduced pressure to a residue. Theresidue was purified by column chromatography on silica gel using50:1-methylene chloride-acetone as an eluent. The appropriate fractionswere combined and concentrated under reduced pressure to a solid. Thesolid was recrystallized from acetone/heptane to yield 1.4 g of1-[4-chloro-2-fluoro-5-[bis(N-methylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ² -1,2,4-triazolin-5-one; m.p. 180°-195° C.

The nmr and the ir spectra were consistent with the proposed structure.

Analysis calc'd for: C₁₂ H₁₂ ClF₃ N₄ O₅ S₂ : C 32.11; H 2.69; N 12.48;Found: C 31.98; H 2.32; N 12.15.

EXAMPLE 3 SYNTHESIS OF1-[4-CHLORO-2-FLUORO-5-(N-METHYLSULFONYLAMINO)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 3)

To a stirred solution of 1.0 g (0.002 mole) of1-[4-chloro-2-fluoro-5-[bis(N-methylsulfonyl)amino]-phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4- triazolin-5-one (prepared as in Example 2) in 25 ml of methanolwas added a solution of 0.17 g (0.004 mole) of sodium hydroxide in 3 mlof water. Upon completion of addition the reaction mixture was stirredfor 15 minutes then poured into 100 ml of water. The mixture wasneutralized with concentrated hydrochloric acid and the solidprecipitate collected by filtration. The solid was dried to yield 0.65 gof1-[4-chloro-2-fluoro-5-(N-methylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one; m.p. 156°-159° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for: C₁₁ H₁₀ ClF₃ N₄ O₃ S: C 34.79; H 2.65; N 14.75;Found: C 35.47; H 2.53; N 14.94.

EXAMPLE 4 SYNTHESIS OF1-[4-CHLORO-2-FLUORO-5-[(N-ETHYLSULFONYL-N-METHYLSULFONYL)AMINO]PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 28)

This compound was prepared in a manner analogous to that of Example 2,using 0.31 g (0.0009 mole) of1-[4-chloro-2-fluoro-5-(N-methylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one, 0.14 g (0.0011 mole) of ethanesulfonyl chloride,and 0.12 g of triethylamine in 5 ml of methylene chloride. The yield of1-[4-chloro-2-fluoro-5-[(N-ethylsulfonyl-N-methylsulfonyl)amino]-phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 0.33 g; m.p. 128°-131.5° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₁₃ H₁₄ ClF₃ N₄ O₅ S₂ : C 33.73; H 3.05; N 12.11;Found: C 33.57; H 3.17; N 12.12.

EXAMPLE 5 SYNTHESIS OF1[4-CHLORO-2-FLUORO-5-[BIS(N-ETHYLSULFONYL)AMINO]PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 38)

This compound was prepared in a manner analogous to that of Example 2using 1.0 g (0.003 mole) of1-(5-amino-4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one (prepared as in Example 1) 0.9 g (0.007 mole) ofethanesulfonyl chloride and 0.7 g (0.007 mole) of triethylamine inmethylene chloride. The yield of1-[4-chloro-2-fluoro-5-[bis(N-ethylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 0.6 g; m.p. 143°-144° C.

The nmr spectrum was consistent with the proposed structure.

The reaction was repeated several times.

EXAMPLE 6 SYNTHESIS OF1-[4-CHLORO-2-FLUORO-5-(N-ETHYLSULFONYLAMINO)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 11)

This compound was prepared in a manner analogous to that of Example 3,using 1.1 g (0.0022 mole) of1-[4-chloro-2-fluoro-5-[bis(N-ethylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 5) and 0.17 g (0.0044mole) of sodium hydroxide in 25 ml of methanol. The yield of1-[4-chloro-2-fluoro-5-(N-ethylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 0.8 g; m.p. 162°-163° C.

The nmr spectrum was consistent with the proposed

Analysis calc'd for: C₁₂ H₁₂ ClF₃ N₄ O₃ S: C 37.46; H 3.14; N 14.56;Found: C 37.65; H 3.12; N 14.44.

EXAMPLE 7 SYNTHESIS OF1-[4-CHLORO-2-FLUORO-5-[(N-ETHYLSULFONYL-N-METHYL)AMINO]PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 29)

To a stirred suspension of 0.095 g (0.0019 mole) of sodium hydride (50%in mineral oil) in dimethylformamide was added 0.7 g (0.0019 mole) of1-[4-chloro-2-fluoro-5-(N-ethylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Examine 6). The reaction mixturewas stirred until homogeneous, approximately 15 minutes. After this time0.28 g (0.002 mole) of methyl iodide was added to the reaction mixture,which was then stirred for 16 hours. The reaction mixture was dilutedwith diethyl ether and washed with water. The organic layer was driedwith sodium sulfate, filtered, and concentrated under reduced pressureto a residue. The residue was purified by column chromatography onsilica gel using 50:1-methylene chloride-acetone as an eluent. Theappropriate fractions were combined and concentrated under reducedpressure to yield 0.7 g of1-[4-chloro-2-fluoro-5-[(N-ethylsulfonyl-N-methyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one; m.p. 101°-103.5° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for: C₁₃ H₁₄ ClF₃ N₄ SO₅ : C 39.15; H 3.54; N 14.05;Found: C 39.46, H 3.57; N 13.91.

EXAMPLE 8 SYMTHESIS OF1-(5-AMINO-4-BROMO-2-FLUOROPHENYL)-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE AS AN INTERMEDIATE Step A Synthesis of PyruvicAcid, 4-Bromo-2-fluorophenylhydrazone as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step D, using 24.3 g (0.128 mole) of commercially available4-bromo-2-fluoroaniline, 11.3 g (0.128 mole) of pyruvic acid, 8.8 g(0.128 mole) of sodium nitrite and 63.2 g (0.28 mole) of stannouschloride in 48 ml of water and 214 ml of concentrated hydrochloric acid.The yield of pyruvic acid, 4-bromo-2-fluorophenylhydrazone was 27.2 g;m.p. 172°-173° C. The reaction was repeated several times.

Step B Synthesis of 1-(4-Bromo-2-fluorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step E. The reaction was run in three batches using a total of 34.3 g(0.125 mole) of pyruvic acid, 4-bromo-2-fluorophenylhydrazone, 35.0(0.127 mole) of diphenylphosphoryl azide, and 12.6 g (0.125 mole) oftriethylamine in 300 ml of toluene. The reaction mixtures were combinedfor isolation of product. The yield of1-(4-bromo-2-fluorophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one was 271.0g, m.p. 201°-203° C.

The nmr spectrum was consistent with the proposed structure. Thereaction was repeated several times.

Step C Synthesis of1-(4-bromo-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step F using 13.0 g (0.048 mole) of1-(4-bromo-2-fluorophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one, 8.0 g(0.143 mole) of powdered potassium hydroxide, 1.6 g (0.005 mole) oftetrabutylammonium bromide, and chlorodifluoromethane in 200 ml oftetrahydrofuran. The yield of1-(4-bromo-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 6.5 g. The reaction was repeated severaltimes.

Step D Synthesis of1-(4-Bromo-2-fluoro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step G using 7.0 g (0.022 mole) of1-(4-bromo-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one and 1.96 ml of 70% nitric acid in 9 ml ofconcentrated sulfuric acid. The yield of1-(4-bromo-2-fluoro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 2.9 g; m.p. 99°-105° C. The reaction wasrepeated several times.

Step E Synthesis of1-(5-amino-4-bromo-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step H using 2.5 g (0.007 mole) of1-(4-bromo-2-fluoro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one and 1.5 g (0.027 mole) of powdered iron in 1 mlof water and 30 ml acetic acid. The yield of1-(5-amino-4-bromo-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 1.7 g; m.p. 117°-119° C.

The nmr spectrum was consistent with the proposed structure.

The reaction was repeated several times.

EXAMPLE 9 SYNTHESIS OF1-[4-BROMO-2-FLUORO-5-[BIS(N-ETHYLSULFONYL)AMINO]PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 40)

This compound was prepared in a manner analogous to that of Example 2using 1.6 g (0.0047 mole) of1-(5-amino-4-bromo-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 8), 1.2 g (0.0095 mole)of ethanesulfonyl chloride, and 1.0 g (0.01 mole) of triethylamine in 24ml of ethylene chloride. The yield of1-[4-bromo-2-fluoro-5-[bis(N-ethylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 0.9 g; m.p. 145°-146° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₁₄ H₁₆ BrF₃ N₄ O₅ S₂ : C 32.25; H 3.09; N 10.75;Found: C 31.94; H 3.10; N 10.78.

EXAMPLE 10 SYNTHESIS OF1-[4-BROMO-2-FLUORO-5-(N-ETHYLSULFONYLAMINO)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5ONE (COMPOUND 13)

This compound was prepared in a manner analogous to that of Example 2using 0.52 g (0.001 mole) of1-[4-bromo-2-fluoro-5-[bis(N-ethylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 9), and 0.1 g (0.0025mole) of sodium hydroxide in 3 ml of water and 40 ml of methanol. Theyield of1-[4-bromo-2-fluoro-5-(N-ethylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 0.38 g; m.p. 140°-141° C.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 11 SYNTHESIS OF1-(5-AMINO-4-BROMO-2-FLUOROPHENYL)-3,4-DIMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE AS AN INTERMEDIATE Step A Synthesis of1-(4-bromo-2-fluorophenyl)-3,4-dimethyl-Δ² -1,2,4-triazolin-5-one as anIntermediate

This compound was prepared in a manner analogous to that of Example 7,using 6.0 g (0.022 mole) of 1-(4-bromo-2-fluorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 8, Step B), 4.1 g (0.029mole) of methyl iodide, and 1.1 g (0.022 mole) of 50% sodium hydride in50 ml of dimethylformamide. The yield of1-(4-bromo-2-fluorophenyl)-3,4-dimethyl-Δ² -1,2,4-triazolin-5-one was3.9 g; m.p. 122°-123.5° C.

The nmr spectrum was consistent with the proposed structure.

Step B Synthesis of 1-(4-Bromo-2-fluoro-5-nitrophenyl)-3,4-dimethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step G using 3.7 g (0.013 mole) of1-(4-bromo-2-fluorophenyl)-3,4-dimethyl-Δ² -1,2,4-triazolin-5-one and0.98 g (0.016 mole) of 70% nitric acid in 15 ml of concentrated sulfuricacid. The yield of 1-(4-bromo-2-fluoro-5-nitrophenyl)-3,4-dimethyl-Δ²-1,2,4-triazolin-5-one was 2.6 g; m.p. 151.5°-154.5° C.

The nmr spectrum was consistent with the proposed structure.

Step C Synthesis of 1-(5-amino-4-bromo-2-fluorophenyl)-3,4-dimethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step H using 2.3 g (0.007 mole) of1-(4-bromo-2-fluoro-5-nitrophenyl)-3,4-dimethyl-Δ²-1,2,4-triazolin-5-one and 2.3 g of powdered iron in 18 ml of water and35 ml of acetic acid. The yield of1-(5-amino-4-bromo-2-fluorophenyl)-3,4-dimethyl-Δ²-1,2,4-triazolin-5-one was 1.2 g; m.p. 151°-155° C.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 12 SYNTHESIS OF1-[4-BROMO-2-FLUORO-5-[BIS(N-ETHYLSULFONYL)AMINO]PHENYL]-3,4-DIMETHYL-.DELTA.²1,2,4-TRIAZOLIN-5-ONE (COMPOUND 39)

This compound was prepared in a manner analogous to that of Example 2,using 0.95 g (0.008 mole) of1-(5-amino-4-bromo-2-fluorophenyl)-3,4-dimethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 11), 1.0 g (0.008 mole)of ethanesulfonyl chloride, and 0.87 g of triethylamine in 25 ml ofmethylene chloride. The yield of1-[4-bromo-2-fluoro-5-[bis(N-ethylsulfonyl)amino]phenyl]-3,4-dimethyl-.DELTA.²-1,2,4-triazolin-5-one was 1.4 g; m.p. 173°-174.5° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for: C₁₄ H₁₈ BrFN₄ O₅ S₂ : C 36.64; H 3.74; N 11.54;Found: C 33.72; H 3.57; N 10.64.

EXAMPLE 13 SYNTHESIS OF1-(5-AMINO-2,4-DICHLOROPHENYL)-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE AS AN INTERMEDIATE Step A Synthesis of PyruvicAcid, 2,4-Dichlorophenylhydrazone as an Intermediate

To a stirred solution of 16.2 g (0.07 mole) of commercially available2,4-dichlorophenylhydrazine hydrochloride in 100 ml of ethanol was addedin one portion 9.2 g (0.11 mole) of pyruvic acid in 100 ml of water. Thereaction mixture was stirred for 10 minutes and the resultant solidcollected by filtration to yield when dried 13.5 g of pyruvic acid,2,4-dichlorophenylhydrazone, m.p. 193°-194° C. The reaction was repeatedseveral times.

Step B Synthesis of 1-(2,4-Dichlorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step E using 13.6 g (0.054 mole) of pyruvic acid,2,4-dichlorophenylhydrazone, 14.9 g (0.054 mole) of diphenylphosphorylazide, and 5.5 g (0.054 mole) of triethylamine in 100 ml of toluene. Theyield of 1-(2,4-dichlorophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one was13.0 g; m.p. 174°-175° C. The reaction was repeated several times.

Step C Synthesis of 1-(2,4-Dichlorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step F using 16.0 g (0.065 mole) of 1-(2,4-dichlorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one, chlorodifluoromethane, 7.3 g (0.13 mole) ofpotassium hydroxide and 10.5 g (0.03 mole) of tetrabutylammonium bromidein 150 ml of tetrahydrofuran. The yield of1-(2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 4.1 g; m.p. 108°-110° C. The reaction wasrepeated several times.

Step D Synthesis of1-(2,4-Dichloro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in the manner of Example 1, Step G using 4.0g (0.013 mole) of 1-(2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one and 1.2 ml (0.015 mole) of 70% nitric acid in 20ml of concentrated sulfuric acid. The yield of1-(2,4-dichloro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was one 3.0 g; m.p. 95°-97° C. The reaction wasrepeated several times.

Step E Synthesis of1-(5-Amino-2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

This compound was prepared in a manner analogous to that of Example 1,Step H using 2.5 g (0.007 mole) of1-(2,4-dichloro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one and 2.5 g (0.045 mole) of powdered iron in 6 mlof water and 60 ml of water. The yield of1-(5-amino-2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 2.0 g; m.p. 133°-135° C. The reaction wasrepeated several times.

EXAMPLE 14 SYNTHESIS OF1-[2,4-DICHLORO-5-[BIS-(N-METHYLSULFONYL)AMINO]PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 22)

This compound was prepared in a manner analogous to that of Example 2using 1.2 g (0.004 mole) of1-(5-amino-2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 13), 0.97 g (0.009 mole)of methanesulfonyl chloride, and 0.95 g (0.009 mole) of triethylamine in15 ml of methylene chloride. The yield of1-[2,4-dichloro-5-[bis(N-methylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 1.3 g; m.p. 213°-214° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for: C₁₂ H₁₂ Cl₂ F₂ N₄ O₅ S₂ : C 30.91; H 2.59; N 12.02;Found: C 31.15; H 2.43; N 12.03.

EXAMPLE 15 SYNTHESIS OF1-[2,4-DICHLORO-5-(N-METHYLSULFONYLAMINO)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 1)

This compound was prepared in a manner analogous to that of Example 3using 0.8 g (0.002 mole) of1-[2,4-dichloro-5-[bis(N-methylsulfonyl)amino]phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 14) and 0.14 g (0.003mole) of sodium hydroxide in 0.3 ml of water and 10 ml of ethanol. Theyield of1-[2,4-dichloro-5-(N-methylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ²-1,2,4-triazolin-5-one was 0.5 g; m.p. 75°-78° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for: C₁₁ H₁₀ Cl₂ F₂ N₄ O₃ S: C 34.21; H 2.59; N 14.51;Found: C 33.98; H 2.62; N 14.20.

EXAMPLE 16 SYNTHESIS OF 1-(5-AMINO-2,4-DICHLOROPHENYL)-3-METHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE AS AN INTERMEDIATE Step A Synthesis of1-(2,4-Dichloro-5-nitrophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one as anIntermediate

This compound was prepared in a manner analogous to that of Example 1,Step G using 6.0 g (0.025 mole) of 1-(2,4-dichlorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one (prepared as an Example 13, Step B) and 1.9 ml(0.03 mole) of 70% nitric acid in 25 ml of concentrated sulfuric acid.The yield of 1-(2,4-dichloro-5-nitrophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one was 5.6 g as a solid.

Step B Synthesis of 1-(5-Amino-2,4-dichlorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one as an Intermediate

To a 500 ml Parr hydrogenation bottle was added 0.5 g of platinum oxide,100 ml of ethanol, then 6.4 g (0.022 mole) of1-(2,4-dichloro-5-nitrophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one. Thebottle was placed in a Parr hydrogenator and the reaction mixture shakenuntil the theoretical amount of hydrogen was taken up. The bottle wasremoved from the hydrogenator and the reaction mixture filtered. Thefiltrate was dried with sodium sulfate and refiltered. The filtrate wasconcentrated under reduced pressure to yield 4.5 g of1-(5-amino-2,4-dichlorophenyl)-3-methyl-Δ² -1,2,4-triazolin-5-one.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 17 SYNTHESIS OF1-[2,4-DICHLORO-5-[BIS(N-ETHYLSULFONYL)AMINO]PHENYL]-3-METHYL-4-ETHYLSULFONYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 36)

This compound was prepared in a manner analogous to that of Example 2,using 0.5 g (0.002 mole) of 1-(5-amino-2,4-dichlorophenyl)-3-methyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 16), 0.8 g (0.006 mole)of ethanesulfonyl chloride and 0.7 g (0.007 mole) of triethylamine in 15ml of methylene chloride. The yield of1-[2,4-dichloro-5-[bis(N-ethylsulfonyl)amino]phenyl]-3-methyl-4-ethylsulfonyl-Δ²-1,2,4-triazolin-5-one was 0.5 g; m.p. 215°-216° C.

The nmr spectrum was consistent with the proposed structure. Thereaction was repeated several times.

Analysis calc'd for: C₁₅ H₂₀ Cl₂ N₄ O₇ S₃ : C 33.64; H, 3.77; N 10.46;Found: C 33.88; H 3.91; N 10.68.

EXAMPLE 18 SYNTHESIS OF1-[2,4-DICHLORO-5-(N-ETHYLSULFONYLAMINO)PHENYL]-3-METHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE

This compound was prepared in a manner analogous to that of Example 3,using 0.9 g (0.002 mole) of1-[2,4-dichloro-5-[bis(N-ethylsulfonyl)amino]phenyl-3-methyl-4-ethylsulfonyl-Δ²-1,2,4-triazolin-5-one (prepared as in Example 17) and 0.2 g (0.005mole) sodium hydroxide in 0.25 ml of water and 12 ml of ethanol. Theyield of 1-[2,4-dichloro-5-(N-ethylsulfonylamino)phenyl]-3-methyl-Δ²-1,2,4-triazolin-5-one was 0.5 g; m.p. 221°-222.5° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for: C₁₀ H₁₀ Cl₂ F₂ N₄ O₃ S: C 34.21; H 2.58; N 13.51;Found: C 33.98; H 2.62; N 14.20.

EXAMPLE 19 SYNTHESIS OF1-[4-CHLORO-2-FLUORO-5-(N-ETHYLSULFONYLAMINO)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Δ²-1,2,4-TRIAZOLIN-5-ONE (COMPOUND 11)

A stirred suspension of 1.0 g (0.0034 mole) of1-(4-amino-4-chloro-2-fluorophenyl)-3-methyl-4-difluoromethyl-Δ.sup.2-1,2,4-triazolin-5-one in 5 ml of methylene chloride was cooled in anice water bath and 0.3 ml (0.0037 mole) of pyridine was added. Uponcompletion of addition 0.33 ml (0.0035 mole) of ethanesulfonyl chloridewas added and the reaction mixture was stirred at 0° C. for one hour.After this time the reaction mixture was allowed to warm to ambienttemperature where it stirred for 16 hours. Analysis of the reactionmixture by thin layer chromatography (TLC) indicated the presence of asmall amount of starting material. An additional 0.05 ml of pyridine and0.05 ml of ethanesulfonyl chloride were added and the reaction mixturewas stirred at ambient temperature for one hour. Analysis of thereaction mixture by TLC indicated that the reaction had gone tocompletion. The reaction mixture was poured into water. The organiclayer was separated and the water layer extracted with methylenechloride. The extracts and the organic layer were combined and washed insuccession with aqueous 1N hydrochloric acid, aqueous saturated sodiumbicarbonate solution, water, and aqueous saturated sodium chloridesolution. The organic layer was dried with magnesium sulfate andfiltered. The filtrate was concentrated under reduced pressure to aresidue. The residue was dried under high vacuum to yield 1.45 g of1-[4-chloro-2-fluoro-5-(N-ethylsulfonylamino)phenyl]-3-methyl-4-difluoromethyl-Δ² -1,2,4-triazolin-5-one as an oily foam. The nmr spectrum wasconsistent with the proposed structure.

EXAMPLE 20 4-CHLORO-2-FLUORO-5-(N-ETHYLSULFONYLAMINO)ANILINE Step A2-Fluoro-5-Nitroacetanilide

To a stirred solution of 18.0 g (0.11 mole) of 2-fluoro-5-nitroanilinein 100 ml of dioxane was added 15.3 g (0.15 mole) of acetic anhydride.The reaction mixture was heated at reflux for two hours. The solvent wasremoved from the mixture by distillation under reduced pressure leavinga solid residue. This residue was stirred in 25 ml of methylene chlorideand filtered. The filter cake was dried to yield 20.5 g of2-fluoro-5-nitroacetanilide, m.p. 177°-178° C.

Step B 5-Amino-2-fluoroacetanilide

Hydrogenation of 20.0 g (0.10 mole) of 2-fluoro-5-nitroacetanilide witha catalytic amount (0.3 g) of platinum oxide in 200 ml of anethanol/ethylacetate (80/20) solution yielded 16.0 g of5-amino-2-fluoroacetanilide as a solid.

Step C 2-Fluoro-bis(N-ethylsulfonylamino)acetanilide

To a stirred mixture of 15.4 g (0.091 mole) of5-amino-2-fluoroacetanilide in 75 ml of methylene chloride was added18.5 g (0.183 mole) of triethyl amine. To this mixture was added slowly23.5 g (0.183 mole) of ethyl sulfonyl chloride. The resultant mixturewas stirred at room temperature for approximately 18 hours. The reactionmixture was passed through a column of silica gel, eluting withmethylene chloride, to yield 12.0 g of2-fluoro-5-bis(N-ethylsulfonylamino)acetanilide.

Steps A-C were repeated to prepare additional2-fluoro-5-bis(N-ethylsulfonylamino)acetanilide.

Step D 2-Fluoro-5-(N-ethylsulfonylamino)acetanilide

To a stirred solution of 27.0 g (0.077 mole) of2-fluoro-5-bis(N-ethylsulfonylamino)acetanilide in 100 ml of dioxane wasadded a solution of sodium hydroxide (5.65 g, (0.0141 mole) in 20 ml ofwater. Approximately 100 ml of water was added and the resultantsolution was stirred at room temperature for about 15 minutes. Thedioxane solvent was removed from the solution by extraction with diethylether. The remaining aqueous phase was acidified with concentratedhydrochloric acid forming a precipitate. The precipitate was collectedby filtration and dried to yield 14.8 g of2-fluoro-5-(N-ethylsulfonylamino)acetanilide, m.p. 175.5°-177° C.Additional product (1.9 g) was collected by extracting the filtrate withethyl acetate and evaporating the extract after drying over anhydrousmagnesium sulfate.

The nmr and ir spectra were consistent with the proposed structure.

Step E 4-Chloro-2-fluoro-5-(N-ethylsulfonylamino)acetanilide

To a stirred solution of 8.0 g (0.031 mole) of2-fluoro-5-(N-ethylsulfonylamino)acetanilide in 200 ml of dioxane wasadded slowly 2.5 ml (0.031 mole) of thionyl chloride. This mixture washeated at 80° C. for two days. The mixture was poured into ice water andthe mixture was extracted with ethyl acetate. The extract was dried overanhydrous magnesium sulfate and filtered. The filtrate was evaporatedunder reduced pressure to yield 8.1 g of4-chloro-2-fluoro-5-(N-ethylsulfonylamino)acetanilide.

Step F 4-Chloro-2-fluoro-5-(N-ethylsulfonylamino)aniline

A stirred mixture of 2.0 g (0.0068 mole) of4-chloro-2-fluoro-5-(N-ethylsulfonylamino)acetanilide and 0.84 g (0.020mole) of sodium hydroxide in 100 ml of water was heated at reflux forapproximately 18 hours. The reaction mixture was cooled and neutralizedwith concentrated hydrochloric acid. The neutralized mixture wasextracted with ethylacetate. The extract was washed with an aqueous,saturated sodium chloride solution. The washed extract was dried overanhydrous magnesium sulfated and filtered. The filtrate was evaporatedunder reduced pressure to yield 2.7 g of4-chloro-2-fluoro-5-(N-ethylsulfonylamino)aniline as a solid.

The nmr was consistent with the proposed structure.

HERBICIDAL ACTIVITY

The plant test species used in demonstrating the herbicidal activity ofcompounds of this invention include cotton (Gossypium hirsutum var.Stoneville), soybean (Glycine max var. Williams), field corn (Zea maysvar. Agway 595S), rice (Oryza sativa var. Labelle), wheat (Triticumaestivium var. Prodax), field bindweed (Convolvulus arvensis),morningglory (Ipomea lacunosa or Ipomea hederacea), velvetleaf (Abutilontheophrasti), barnyardgrass (Echinochloa crus galli), green foxtail(Setaria viridis), and johnsongrass (Sorghum halepense).

Seeds or tubers of the plant test species were planted in furrows insteam sterilized sandy loam soil contained in disposable fiber flats. Atopping soil of equal portions of sand and sandy loam soil was placeduniformly on top of each flat to a depth of approximately 0.5 cm.

The flats for the preemergence test were watered, then drenched with theappropriate amount of a solution of the test compound in a 50/50 mixtureof acetone and water containing a small amount (up to 0.5% v/v) ofsorbitan monolaurate emulsifier/solubilizer. The concentration of thetest compound in solution was varied to give a range of applicationrates, generally 8.0 kg/ha and submultiples thereof. The flats wereplaced in a greenhouse and watered regularly at the soil surface for 21days at which time phytotoxicity data were recorded.

The flats for the postemergence test were placed in a greenhouse andwatered for 8-10 days, then the foliage of the emerged test plants wassprayed with a solution of the test compound in acetone-water containingup to 0.5% sorbitan monolaurate. After spraying the foliage was kept dryfor 24 hours, then watered regularly for 21 days, and phytotoxicity datarecorded.

Phytotoxicity data were taken as percent control. Percent control wasdetermined by a method similar to the 0 to 100 rating system disclosedin "Research Methods In Weed Science," 2nd ed., B. Truelove, Ed.;Southern Weed Science Society; Auburn University, Auburn, Ala., 1977.The present rating system is as follows:

    ______________________________________                                        Herbicide Rating System                                                       Rating Description                                                            Percent                                                                              of Main   Crop           Weed                                          Control                                                                              Categories                                                                              Description    Description                                   ______________________________________                                         0     No effect No crop reduction                                                                            No weed control                                                or injury                                                    10     Slight    Slight discolora-                                                                            Very poor weed                                       effect    tion or stunting                                                                             control                                       20               Some discolora-                                                                              Poor weed                                                      tion, stunting or                                                                            control                                                        stand loss                                                   30               Crop injury more                                                                             Poor to defi-                                                  pronounced but not                                                                           cient weed                                                     lasting        control                                       40     Moderate  Moderate injury,                                                                             Deficient weed                                       effect    crop usually   control                                                        recovers                                                     50               Crop injury more                                                                             Deficient to                                                   lasting, recovery                                                                            moderate weed                                                                 control                                       60               Lasting crop   Moderate weed                                                  injury no recovery                                                                           control                                       70     Severe    Heavy injury and                                                                             Control some-                                        effect    stand loss     what less than                                                                satisfactory                                  80               Crop nearly des-                                                                             Satisfactory                                                   troyed a few   to good weed                                                   survivors      control                                       90               Only occasional                                                                              Very good to                                                   live plants left                                                                             excellent                                                                     control                                       100    Complete  Complete crop  Complete weed                                        effect    destruction    destruction                                   ______________________________________                                    

Herbicidal data at selected application rates are given for variouscompounds of the invention in Table 3 and 4 below. The test compoundsare identified in the tables below by numbers which correspond to thosein Table 1.

In the tables of herbicidal data below:

"kg/ha" is kilograms per hectare, and

"% C" is percent control.

It is clear that the generic class of aryltriazolinones and thiones andthiones described and illustrated herein is characterized by herbicidalactivity, and that the degree of this activity varies among specificcompounds within this class and to some extent among the species ofplant to which these compounds may be applied. Thus, selection of aspecific herbicidal compound for control of a specific plant may readilybe made.

For herbicidal application, the active compounds as above defined areformulated into herbicidal compositions, by admixture, in herbicidallyeffective amounts, with adjuvants and carriers normally employed in theart for facilitating the dispersion of active ingredients for theparticular utility desired, recognizing the fact that the formulationand mode of application of a toxicant may affect the activity of thematerial in a given application. Thus, for agricultural use the presentherbicidal compounds may be formulated as granules of relatively largeparticle size, as water-soluble or water-dispersible granules, aspowdery dusts, as wettable powders, as emulsifiable concentrates, assolutions, or as any of several other known types of formulations,depending on the desired mode of application.

For preemergence application these herbicidal compositions are usuallyapplied either as sprays, dusts, or granules in the areas in whichsuppression of vegetation is desired. For postemergence control ofestablished plant growth, sprays or dusts are most commonly used. Theseformulations may contain as little as 0.5% to as much as 95% or more byweight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finelydivided solids such as talc, natural clays, kieselguhr, flours such aswalnut shell and cottonseed flours, and other organic and inorganicsolids which act as dispersants and carriers for the toxicant; thesefinely divided solids have an average particle size of less than about50 microns. A typical dust formulation useful herein is one containing1.0 part of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- andpostemergence herbicides, are in the form of finely divided particleswhich disperse readily in water or other dispersant. The wettable powderis ultimately applied to the soil either as a dry dust or as an emulsionin water or other liquid. Typical carriers for wettable powders includeFuller's earth, kaolin clays, silicas, and other highly absorbent,readily wet inorganic diluents. Wettable powders normally are preparedto contain about 5-80% of active ingredient, depending on the absorbencyof the carrier, and usually also contain a small amount of a wetting,dispersing or emulsifying agent to facilitate dispersion. For example, auseful wettable powder formulation contains 80.8 parts of the herbicidalcompound, 17.9 parts of Palmetto clay, and 1.0 part of sodiumlignosulfonate and 0.3 part of sulfonated aliphatic polyester as wettingagents. Frequently, additional wetting agent and/or oil will be added tothe tank-mix for postemergence application to facilitate dispersion onthe foliage and absorption by the plant.

Other useful formulations for herbicidal applications are emulsifiableconcentrates. Emulsifiable concentrates are homogeneous liquid or pastecompositions dispersible in water or other dispersant, and may consistentirely of the herbicidal compound and a liquid or solid emulsifyingagent, or may also contain a liquid carrier, such as xylene, heavyaromatic naphthas, isophorone, or other non-volatile organic solvent.For herbicidal application these concentrates are dispersed in water orother liquid carrier, and normally applied as a spray to the area to betreated. The percentage by weight of the essential active ingredient mayvary according to the manner in which the composition is to be applied,but in general comprises 0.5 to 95% of active ingredient by weight ofthe herbicidal composition.

Typical wetting, dispersing, or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their sodium salts, polyhydric alcohols, and othertypes of surface active agents, many of which are available in commerce.The surface active agent, when used, normally comprises 1% to 15% byweight of the herbicidal composition.

For instance an emulsifiable concentrate may have the followingcomposition (in % by weight):

    ______________________________________                                        Active ingredient    40.00                                                    Antimicrobial agent  0.05                                                     Foam suppressant     0.10                                                     Surfactant C         2.60                                                     Surfactant D         0.40                                                     Thickener            0.35                                                     Suspending agent     0.45                                                     Propylene glycol (antifreeze)                                                                      6.00                                                     Water                50.05                                                    Total                100.00                                                   ______________________________________                                    

The antimicrobial agent is sodium o-phenylphenate tetrahydrate soldunder the trademark and designation "Dowacide A". The foam suppressantis a water dilutable silicone emulsion sold under the trademark anddesignation "Dow Corning AF". Surfactant C is a non-ionic paste of acondensate of ethylene oxide with a hydrophobic base formed bycondensing propylene oxide with propylene glycol, sold under thetrademark and designation "Pluronic P-84." Surfactant D is an anionicliquid comprising the sodium salt of a complex organic phosphate ester,sold under the trademark and designation "GAFAC LO-529." The thickeneris a xanthan gum sold under the trademark and designation "Kelzan-M".The suspending agent is a colloidal magnesium aluminum silicate soldunder the trademark and designation "Veegum." In use, by the farmer,this concentrate may be diluted with water to provide an aqueouscomposition containing, say about 1/4% to 11/2% of the activeingredient, for use on the field.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Thus asuitable solution may contain, for instance, some 65% of the activeingredient, together with a minor proportion (say 1 to 10%) of asurfactant; for use on the field, this solution may be diluted withwater, by the farmer, to provide an aqueous composition containing, sayabout 1/4% to 11/2% of the active ingredient. Granular formulations,wherein the toxicant is carried on relatively coarse particles, are ofparticular utility for aerial distribution or for penetration of covercrop canopy. Pressurized sprays, typically aerosols wherein the activeingredient is dispersed in finely divided form as a result ofvaporization of a low boiling dispersant solvent carrier, such as theFreons, may also be used. Water-soluble or water-dispersible granulesare also useful formulations for herbicidal application of the presentcompounds. Such granular formulations are free-flowing, non-dusty, andreadily water-soluble or water-miscible. The soluble or dispersiblegranular formulations described in U.S. Pat. No. 3,920,442 are usefulherein with the present herbicidal compounds; these may be diluted withwater, by the former, to provide an aqueous composition containing sayabout 1/4 to 11/2% of the active ingredient, for use on the field.

The active herbicidal compounds of this invention may be formulatedand/or applied with insecticides, fungicides, nematicides, plant growthregulators, fertilizers, or other agricultural chemicals and may be usedas effective soil sterilants as well as selective herbicides inagriculture. In applying an active compound of this invention, whetherformulated alone or with other agricultural chemicals, an effectiveamount and concentration of the active compound is of course employed;the amount may be as low as 15 g/ha or lower, e.g. about 10 to 500 g/hasuch as 50, 100, 200 or 300 g/ha.

The active herbicidal compounds of this invention may be used incombination with other herbicides, e.g. they may be mixed with, say, anequal or larger amount of a known herbicide such as chloroacetanilideherbicides such as2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor),2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide(metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine(diethatyl-ethyl); benzothiadiazinone herbicides such as3-(1-methylethyl)(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide(bentazon); triazine herbicides such as6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine(atrazine), and2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropanenitrile(cyanazine); dinitrolaniline herbicides such as2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin);and aryl urea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluometuron); and otherheterocyclic nitrogen herbicides such as2-(2-(chlorophenyl)methyl)-4,4-dimethyl-3-isoxazolidinone.

It is apparent that various modifications may be made in the formulationand application of the compounds of this invention without departingfrom the inventive concepts herein as defined in the claims.

                                      TABLE 1                                     __________________________________________________________________________    Representative Compounds                                                       ##STR15##                                                                    Cpd                                                                              X  Y    R          R.sup.1 R.sup.2                                                                            R.sup.3                                    __________________________________________________________________________     1 Cl Cl   CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                    2 F  F    CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                    3 F  Cl   CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                    4 F  Br   CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                    5 F  CH.sub.3                                                                           CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                    6 CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                    9 Cl Cl   C.sub.2 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   10 F  F    C.sub.2 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   11 F  Cl   C.sub.2 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   12 F  Br   C.sub.2 H.sub. 5                                                                         H       CH.sub.3                                                                           CH.sub.3                                   13 F  Br   C.sub.2 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   14 CH.sub.3                                                                         CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   15 F  Br   C.sub.2 H.sub.5                                                                          H       (CH.sub.2).sub.3 F                                                                 CH.sub.3                                   16 Cl Cl    -n-C.sub.3 H.sub.7                                                                      H       CHF.sub.2                                                                          CH.sub.3                                   17 F  F     -n-C.sub.3 H.sub.7                                                                      H       CHF.sub.2                                                                          CH.sub.3                                   18 F  Cl    -n-C.sub.3 H.sub.7                                                                      H       CHF.sub.2                                                                          CH.sub.3                                   19 F  Br    -n-C.sub.3 H.sub.7                                                                      H       CHF.sub.2                                                                          CH.sub.3                                   20 F  Cl   CH.sub.3   C.sub.2 H.sub.5                                                                       CHF.sub.2                                                                          CH.sub.3                                   21 F  Cl   CH.sub.3    -n-C.sub.3 H.sub.7                                                                   CHF.sub.2                                                                          CH.sub.3                                   22 Cl Cl   CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   23 F  F    CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   24 F  Cl   CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   25 F  Br   CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   26 F  CH.sub.3                                                                           CH.sub.3   SO.sub. 2 CH.sub.3                                                                    CHF.sub.2                                                                          CH.sub.3                                   27 CH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   28 F  Cl   CH.sub.3   SO.sub.2 CH.sub.5                                                                     CHF.sub.2                                                                          CH.sub.3                                   29 F  Cl   C.sub.2 H.sub.5                                                                          CH.sub.3                                                                              CHF.sub.2                                                                          CH.sub.3                                   30 F  Cl   C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                       CHF.sub.2                                                                          CH.sub.3                                   31 F  Cl   C.sub.2 H.sub.5                                                                           -n-C.sub.3 H.sub.7                                                                   CHF.sub.2                                                                          CH.sub.3                                   32 F  Cl   C.sub.2 H.sub.5                                                                           .sub.-i-C.sub.3 H.sub.7                                                              CHF.sub.2                                                                          CH.sub.3                                   33 F  Cl   C.sub.2 H.sub.5                                                                          CH.sub.2 OCH.sub.3                                                                    CHF.sub.2                                                                          CH.sub.3                                   35 Cl Cl   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CHF.sub.2                                                                          CH.sub.3                                   36 Cl Cl   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              SO.sub.2 C.sub.2 H.sub.5                                                           CH.sub.3                                   37 F  F    C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CHF.sub.2                                                                          CH.sub.3                                   38 F  Cl   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CHF.sub.2                                                                          CH.sub.3                                   39 F  Br   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                           CH.sub.3                                   40 F  Br   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CHF.sub.2                                                                          CH.sub.3                                   41 CH.sub.3                                                                         CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CHF.sub.2                                                                          CH.sub.3                                   42 F  Br   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              (CH.sub.2).sub.3 F                                                                 CH.sub.3                                   43 Cl Cl    -n-C.sub.3 H.sub.7                                                                      SO.sub.2 C.sub.3 H.sub.7 ( -n)                                                        CHF.sub.2                                                                          CH.sub.3                                   44 F  F     -n-C.sub.3 H.sub.7                                                                      SO.sub.2 C.sub.3 H.sub.7 ( -n)                                                        CHF.sub.2                                                                          CH.sub.3                                   45 F  Cl    -n-C.sub.3 H.sub.7                                                                      SO.sub.2 C.sub.3 H.sub.7 ( -n)                                                        CHF.sub.2                                                                          CH.sub.3                                   46 F  Br    -n-C.sub.3 H.sub.7                                                                      SO.sub.2 C.sub.3 H.sub.7 ( -n)                                                        CHF.sub.2                                                                          CH.sub.3                                   47 F  Cl   CH.sub.3   CH.sub.3                                                                              CHF.sub.2                                                                          CH.sub.3                                   48 F  Cl   CF.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   49 F  Cl   CH.sub.3   C.sub.4 H.sub.9                                                                       CHF.sub.2                                                                          CH.sub.3                                   50 Cl Cl   CH.sub.3   C.sub.2 H.sub.5                                                                       CHF.sub.2                                                                          CH.sub.3                                   51 Cl Cl   CH.sub.3   C.sub.3 H.sub.7                                                                       CHF.sub.2                                                                          CH.sub.3                                   52 Cl Cl   CH.sub.3   C.sub.4 H.sub.9                                                                       CHF.sub.2                                                                          CH.sub.3                                   53 F  Cl   C.sub.6 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   54 F  Cl   N(CH.sub.3).sub.2                                                                        H       CHF.sub.2                                                                          CH.sub.3                                   55 F  Cl   N(C.sub.2 H.sub.5).sub.2                                                                 H       CHF.sub.2                                                                          CH.sub.3                                   56 F  Cl   OH         H       CHF.sub.2                                                                          CH.sub.3                                   57 F  Cl   CH.sub.3   CHF.sub.2                                                                             CHF.sub.2                                                                          CH.sub.3                                   58 Cl F    CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   59 Cl F    C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.2 H.sub.5                                                              CHF.sub.2                                                                          CH.sub.3                                   60 Cl F    CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   61 Cl F    C.sub.2 H.sub.5                                                                          H       CHF.sub.2                                                                          CH.sub.3                                   62 CH.sub.3                                                                         Cl   CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   63 CH.sub.3                                                                         Cl   CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   64 F  NO.sub.2                                                                           CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   65 F  NO.sub.2                                                                           CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   66 F  OCHF.sub.2                                                                         CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   67 F  OCHF.sub.2                                                                         CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   68 F  CF.sub.3                                                                           CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          CH.sub.3                                   69 F  CF.sub.3                                                                           CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   70 F  Cl   (CH.sub.2).sub.3   CHF.sub.2                                                                          CH.sub.3                                   71 F  Cl   (CH.sub.2).sub.4   CHF.sub.2                                                                          CH.sub.3                                   72 F  Cl   (CH.sub.2).sub.5   CHF.sub.2                                                                          CH.sub.3                                   73 F  Cl   (CH.sub.2).sub.6   CHF.sub.2                                                                          CH.sub.3                                   74 F  Cl   CH.sub.2 COOH                                                                            H       CHF.sub.2                                                                          CH.sub.3                                   75 F  Cl   CH.sub.3   OCH.sub.3                                                                             CHF.sub.2                                                                          CH.sub.3                                   76 F  Cl   CH.sub.3   CH.sub.2 CH.sub.2 CH.sub.2 F                                                          CHF.sub.2                                                                          CH.sub.3                                   77 F  Cl   CH.sub.3   H       CHF.sub.2                                                                          OCH.sub.3                                  78 F  Cl   CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          OCH.sub.3                                  79 F  Cl   CH.sub.3   SO.sub.2 CH.sub.3                                                                     CHF.sub.2                                                                          Cl                                         80 F  Cl   CH.sub.3   H       CHF.sub.2                                                                          Cl                                         81 F  Cl   CH.sub. 3  H       CHF.sub.2                                                                          H                                          82 F  Cl   CH.sub.3   H       CHF.sub.2                                                                          SO.sub.2 CH.sub.3                          83 F  Cl   CH.sub.3   H       CHF.sub.2                                                                          SOCH.sub.3                                 84 F  Cl   CH.sub.3   H       CHF.sub.2                                                                          SCH.sub.3                                  85 F  Cl                                                                                  ##STR16## H       CHF.sub.2                                                                          CH.sub.3                                   86 F  Cl                                                                                  ##STR17## H       CHF.sub.2                                                                          CH.sub.3                                   87 F  Cl                                                                                  ##STR18## H       CHF.sub.2                                                                          CH.sub.3                                   88 Br Cl   CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   89 Br Br   CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   90 Br CF.sub.3                                                                           CH.sub.3   H       CHF.sub.2                                                                          CH.sub.3                                   __________________________________________________________________________     Other representative compounds are those which are identical with             compounds 20, 21, 29-33 and 47-87 91-97 respectively, except that X is F      and Y is Br. Still other representative compounds are those which are         identical with Compounds 1 to 87 91-97 respectively, except that X is F       and Y is CF.sub.3. Other representative compounds are those that are          identical to compounds 9 to 87 respectively, except that X is Br. Other       representative compounds are those which are identical with Compounds         1-19, 48, 53-56, 60, 61, 63, 65, 67, 69, 71, 74, 77, 80-97, respectively,     except that R.sup.1 is Na (or other saltforming group).                       Compounds in which R.sup.1 is H, such as compound 1, used preemergently       have shown a selectivity favorable to soybeans. Compounds in which R.sup.     is alkyl, such as compound 31, used preemergently, have shown a               selectivity favorable to cotton. Compound 1 preemergently applied also        shows good corn tolerance. These are effective at low rates of                application.                                                             

                  TABLE 2                                                         ______________________________________                                        Characterizing Data                                                                                       Elemental                                         Cmpd                        Analysis                                          No.   M.P. (°C.)                                                                       Empirical Formula                                                                             C    H    N                                   ______________________________________                                        1     75-78     C.sub.11 H.sub.10 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                                          C   34.21                                                                              2.59 14.51                                   (d)*                    F   33.98                                                                              2.62 14.20                             2     160-161   C.sub.11 H.sub.10 F.sub.4 N.sub.4 O.sub.3 S                                                 C   37.29                                                                              2.85 15.81                                                           F   37.33                                                                              2.75 16.00                             3     156-159   C.sub.11 H.sub.10 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   34.79                                                                              2.65 14.75                                                           F   35.47                                                                              2.53 14.94                             4     162-163   C.sub.11 H.sub.10 BrF.sub.3 N.sub.4 O.sub.3 S                                               C   31.82                                                                              2.43 13.49                                                           F   31.93                                                                              2.31 13.28                             5     136-138   C.sub.13 H.sub.13 F.sub.3 N.sub.4 O.sub.3 S                                                 C   41.14                                                                              3.74 15.99                                                           F   41.20                                                                              3.88 15.74                             6     140-141   C.sub.13 H.sub.16 F.sub.2 N.sub.4 O.sub.3 S                   9     126-128   C.sub.12 H.sub.12 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                                          C   35.92                                                                              3.02 13.96                                                           F   35.83                                                                              3.00 13.95                             10    118-119   C.sub.12 H.sub.12 F.sub.4 N.sub.4 O.sub.3 S                                                 C   39.13                                                                              3.28 15.21                                                           F   38.92                                                                              3.44 15.20                             11    162-163   C.sub.12 H.sub.12 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   37.46                                                                              3.14 14.56                                                           F   37.65                                                                              3.12 14.44                             12    218.5-220 C.sub.12 H.sub.14 BrFN.sub.4 O.sub.3 S                                                      C   36.65                                                                              3.59 14.25                                                           F   36.94                                                                              3.48 14.17                             13    140-141   C.sub.12 H.sub.12 BrF.sub.3 N.sub.4 O.sub.3 S                 14    123-124   C.sub.14 H.sub.18 F.sub.2 N.sub.4 O.sub.3 S                   15    152-153   C.sub.14 H.sub.17 BrF.sub.2 N.sub.4 O.sub.3 S                                               C   38.28                                                                              3.90 12.75                                                           F   38.33                                                                              3.92 12.60                             16    159-162   C.sub.12 H.sub.14 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                                          C   37.60                                                                              3.40 13.49                                                           F   37.60                                                                              3.15 13.53                             17    107-108   C.sub.13 H.sub.14 F.sub.4 N.sub.4 O.sub.3 S                                                 C   40.84                                                                              3.70 14.65                                                           F   40.54                                                                              3.47 14.51                             18    95-96     C.sub.13 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   39.18                                                                              3.54 14.05                                                           F   38.07                                                                              3.60 14.05                             19    114-115   C.sub.13 H.sub.14 BrF.sub.3 N.sub.4 O.sub.3 S                 20    112-116   C.sub.13 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3 S                 21    108-111   C.sub.14 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3 S                 22    213-214   C.sub.12 H.sub.12 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5                            S.sub.2       C   30.91                                                                              2.59 12.02                                                           F   31.15                                                                              2.43 12.03                             23    175-180   C.sub.12 H.sub.12 F.sub.4 N.sub.4 O.sub.5 S.sub.2                                           C   33.33                                                                              2.80 12.96                                                           F   33.25                                                                              2.85 12.93                             24    180-196   C.sub.12 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S.sub.2                                         C   32.11                                                                              2.69 12.98                                                           F   31.98                                                                              2.32 12.15                             25    192-194   C.sub.12 H.sub.12 F.sub.3 N.sub.4 O.sub.5 S.sub.2                                           C   29.22                                                                              2.45 11.36                                                           F   29.19                                                                              2.42 11.32                             26    172-176   C.sub.13 H.sub.15 F.sub.3 N.sub.4 O.sub.5 S.sub.2             27    208-209   C.sub.14 H.sub.18 F.sub.2 N.sub.4 O.sub.5 S.sub.2             28    128-131   C.sub.13 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S.sub.2                                         C   33.73                                                                              3.05 12.11                                                           F   33.57                                                                              3.17 12.12                             29    101-104   C.sub.13 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   39.15                                                                              3.54 14.05                                                           F   39.46                                                                              3.57 13.91                             30    114-115   C.sub.14 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   40.73                                                                              3.91 13.57                                                           F   41.05                                                                              3.74 13.46                             31    135-137   C.sub.15 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   42.21                                                                              4.25 13.13                                                           F   42.02                                                                              4.28 12.95                             32    125-126   C.sub.15 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   42.21                                                                              4.25 12.12                                                           F   43.05                                                                              4.30 12.81                             33    126-128   C.sub.14 H.sub.16 ClF.sub.3 N.sub.4 O.sub.4 S                                               C   39.21                                                                              3.76 13.07                                                           F   39.98                                                                              3.77 12.87                             35    159-160   C.sub.14 H.sub.16 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5                            S.sub.2                                                       36    215-216   C.sub.15 H.sub.20 Cl.sub.2 N.sub.4 O.sub.7 S.sub.3                                          C   33.64                                                                              3.77 10.46                                                           F   33.88                                                                              3.91 10.68                             37    145-147   C.sub.14 H.sub.16 F.sub.4 N.sub.4 O.sub.5 S.sub.2                                           C   36.52                                                                              3.50 12.17                                                           F   36.48                                                                              3.53 12.04                             38    143-144   C.sub.14 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5 S.sub.2           39      173-174.5                                                                             C.sub.14 H.sub.18 BrFN.sub.4 O.sub.5 S.sub.2                                                C   34.64                                                                              3.74 11.54                                                           F   33.72                                                                              3.57 10.64                             40    145-146   C.sub.14 H.sub.16 BrF.sub.3 N.sub.4 O.sub.5 S.sub.2                                         C   32.25                                                                              3.09 10.75                                                           F   31.94                                                                              3.10 10.78                             41    169-172   C.sub.16 H.sub.22 F.sub.2 N.sub.4 O.sub.5 S.sub.2             42    151-153   C.sub.16 H.sub.21 BrF.sub.2 N.sub.4 O.sub.5 S.sub.2                                         C   36.16                                                                              3.98 10.54                                                           F   35.68                                                                              3.68 10.12                             43    168-169   C.sub.16 H.sub.20 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5                            S.sub.2       C   36.86                                                                              3.87 10.75                                                           F   37.01                                                                              3.90 10.94                             44    64-67     C.sub.16 H.sub.20 F.sub.4 N.sub.4 O.sub.5 S.sub.2                                           C   39.34                                                                              4.13 11.47                                                           F   39.27                                                                              4.05 11.27                             45    119-121   C.sub.16 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5 S.sub.2                                         C   38.06                                                                              3.99 11.10                                                           F   38.11                                                                              3.97 10.89                             46    128-129   C.sub.16 H.sub.20 BrF.sub.3 N.sub.4 O.sub.5 S.sub.2                                         C   34.98                                                                              3.67 10.20                                                           F   35.00                                                                              3.61 10.12                             47    oil       C.sub.12 H.sub.12 ClF.sub.3 N.sub.4 O.sub.3 S                 48    172-173   C.sub.11 H.sub.7 ClF.sub.6 N.sub.4 O.sub.3 S                                                C   31.12                                                                              1.66 13.19                                                           F   30.86                                                                              1.61 12.99                             49    oil       C.sub.15 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3 S                 50    125-126   C.sub.13 H.sub.14 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                                          C   37.60                                                                              3.40 13.49                                                           F   37.78                                                                              3.34 13.23                             51    oil       C.sub.14 H.sub.16 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                                          C   39.17                                                                              3.76 13.05                                                           F   39.26                                                                              3.70 12.80                             52    oil       C.sub.15 H.sub.18 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                                          C   40.64                                                                              4.09 12.64                                                           F   40.38                                                                              4.32 12.34                             93    122-124   C.sub.18 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   46.91                                                                              3.50 12.16                                                           F   46.85                                                                              3.65 11.88                             94    solid     C.sub.18 H.sub.14 Cl.sub.3 F.sub.3 N.sub.4 O.sub.3                                          C   40.81                                                                              2.66 10.58                                                           F   41.27                                                                              2.55 10.19                             96    100-101   C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3 S                                               C   40.93                                                                              3.43 13.63                                                           F   40.69                                                                              3.48 13.53                             ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________    Preemergence Herbicidal Activity (% Control)                                  __________________________________________________________________________             Compound No.                                                                  1  2  3  4  5  6  9  10 11 12  13 14                                                                              15 16 17 18 19 20                         Rate (kg/ha)                                                         Species  0.5                                                                              1.0                                                                              0.25                                                                             0.25                                                                             0.5                                                                              1.0                                                                              0.5                                                                              1.0                                                                              0.25                                                                             0.25                                                                              0.25                                                                             1.0                                                                             0.5                                                                              2.0                                                                              1.0                                                                              0.25                                                                             0.25                                                                             0.25              __________________________________________________________________________    Cotton   95 100                                                                              100                                                                              100                                                                              95 40 100                                                                              90 100                                                                              50  95 40                                                                              90 90 90 70 80 95                Soybean  50 60 50 50 80 60 20 30 40 10  30 40                                                                              10 10 30 10 30 95                Field Corn                                                                             100                                                                              10 95 100                                                                              100                                                                              70 95 20 95 10  80 80                                                                              90 90 40 95 95 100               Rice     95 10 90 100                                                                              100                                                                              50 80 10 95 60  90 30                                                                              80 80 70 70 80 100               Wheat    50 20 90 90 95 30 20 10 30 0   40 30                                                                              20 20 20 20 10 95                Field Bindweed                                                                         100                                                                              50 100                                                                              100                                                                              95 100                                                                              100                                                                              80 100                                                                              60  100                                                                              90                                                                              90 100                                                                              60 100                                                                              100                                                                              100               Morningglory                                                                           95 90 90 95 100                                                                              70 95 90 100                                                                              70  100                                                                              70                                                                              100                                                                              100                                                                              80 70 70 100               Velvetleaf                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              80  100                                                                              90                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100               Barnyardgrass                                                                          95 80 95 100                                                                              100                                                                              95 80 70 100                                                                              10  100                                                                              90                                                                              100                                                                              95 70 80 95 100               Green Foxtail                                                                          100                                                                              90 90 100                                                                              100                                                                              100                                                                              70 100                                                                              100                                                                              30  100                                                                              90                                                                              95 95 30 70 95 100               Johnsongrass                                                                           95 70 90 95 100                                                                              90 80 70 90 50  90 90                                                                              90 70 50 70 70 100               __________________________________________________________________________             Compound No.                                                                  21 22 23 24 25 26 27 28 29 30 31  32 33 35 36                                                                              37 38 39                         Rate (kg/ha)                                                         Species  0.25                                                                             0.5                                                                              0.25                                                                             0.25                                                                             0.25                                                                             0.5                                                                              1.0                                                                              0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                              0.5                                                                              0.25                                                                             1.0                                                                              4.0                                                                             0.25                                                                             1.0                                                                              0.25              __________________________________________________________________________    Cotton   95 95 95 100                                                                              95 95 40 100                                                                              90 100                                                                              90  100                                                                              100                                                                              100                                                                              0 80 100                                                                              40                Soybean  100                                                                              70 30 90 100                                                                              100                                                                              80 90 90 100                                                                              100 95 100                                                                              80 0 40 100                                                                              20                Field Corn                                                                             100                                                                              90 20 100                                                                              95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              0 90 100                                                                              50                Rice     100                                                                              90 10 100                                                                              95 95 20 100                                                                              95 95 100 100                                                                              100                                                                              80 10                                                                              50 100                                                                              20                Wheat    100                                                                              80 20 95 95 100                                                                              40 95 80 90 100 100                                                                              100                                                                              95 0 80 100                                                                              10                Field Bindweed                                                                         100                                                                              100                                                                              30 95 80 100                                                                              80 100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              0 70 100                                                                              40                Morningglory                                                                           100                                                                              100                                                                              70 100                                                                              100                                                                              95 60 100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              0 90 100                                                                              60                Velvetleaf                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              0 100                                                                              100                                                                              95                Barnyardgrass                                                                          100                                                                              100                                                                              70 100                                                                              100                                                                              100                                                                              80 100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              10                                                                              95 100                                                                              30                Green Foxtail                                                                          100                                                                              100                                                                              40 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              20                                                                              100                                                                              100                                                                              30                Johnsongrass                                                                           100                                                                              100                                                                              60 100                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              20                                                                              95 100                                                                              90                __________________________________________________________________________                             Compound No.                                                                  40 41 42 43                                                                              44 45 46 47 48 49 93 94 96                                         Rate (kg/ha)                                                          Species 1.0                                                                              1.0                                                                              0.25                                                                             0.5                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             2.0                                                                              0.25                                                                             2.0                                                                              2.0                                                                              0.25              __________________________________________________________________________                     Cotton  100                                                                              30 80 10                                                                              0  30 30 95 100                                                                              80 95 80 95                                 Soybean 90 40 80 10                                                                              0  30 80 95 20 100                                                                              80 10 95                                 Field Corn                                                                            95 100                                                                              100                                                                              70                                                                              95 100                                                                              100                                                                              95 60 100                                                                              100                                                                              90 95                                 Rice    95 40 80 20                                                                              60 80 50 95 80 95 95 50 95                                 Wheat   100                                                                              40 30 10                                                                              70 70 70 95 30 100                                                                              100                                                                              50 95                                 Field Bindweed                                                                        100                                                                              90 70 30                                                                              60 50 90 100                                                                              100                                                                              100                                                                              -- -- --                                 Morningglory                                                                          100                                                                              80 100                                                                              50                                                                              60 80 95 100                                                                              100                                                                              100                                                                              100                                                                              90 100                                Velvetleaf                                                                            100                                                                              90 100                                                                              20                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                Barnyardgrass                                                                         100                                                                              100                                                                              95 80                                                                              90 100                                                                              90 100                                                                              100                                                                              100                                                                              100                                                                              95 100                                Green Foxtail                                                                         100                                                                              100                                                                              90 90                                                                              90 95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              95 100                                Johnsongrass                                                                          100                                                                              95 95 70                                                                              90 95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              95 100               __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Postemergence Herbicidal Activity (% Control)                                 __________________________________________________________________________             Compound No.                                                                  1  2  3  4  5  6 9  10 11 12 13 14                                                                              15 16 17                                                                              18 19 20 21                         Rate (kg/ha)                                                         Species  0.5                                                                              1.0                                                                              0.25                                                                             0.25                                                                             0.5                                                                              1.0                                                                             0.5                                                                              1.0                                                                              0.25                                                                             0.25                                                                             0.25                                                                             1.0                                                                             0.5                                                                              2.0                                                                              1.0                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.25              __________________________________________________________________________    Cotton   100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              80                                                                              100                                                                              100                                                                              100                                                                              30 90 70                                                                              100                                                                              100                                                                              60                                                                              60 100                                                                              100 100              Soybean  60 80 60 80 80 60                                                                              40 70 80 40 70 50                                                                              70 40 40                                                                              50 70 95  100              Field Corn                                                                             40 30 70 80 70 50                                                                              40 30 60 20 90 30                                                                              70 100                                                                              20                                                                              40 80 100 100              Rice     95 20 90 95 80 50                                                                              90 20 90 40 80 20                                                                              50 80 30                                                                              80 70 100 100              Wheat    80 40 50 70 80 40                                                                              80 40 50 10 30 30                                                                              100                                                                              40 30                                                                              30 30 80  100              Field Bindweed                                                                         100                                                                              60 80 95 100                                                                              50                                                                              100                                                                              40 100                                                                              10 100                                                                              70                                                                              80 100                                                                              50                                                                              80 90 100 100              Morningglory                                                                           100                                                                              95 100                                                                              95 95 95                                                                              100                                                                              90 95 30 100                                                                              90                                                                              90 100                                                                              80                                                                              70 90 100 100              Velvetleaf                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              50                                                                              100                                                                              100                                                                              100                                                                              10 100                                                                              50                                                                              100                                                                              100                                                                              70                                                                              100                                                                              100                                                                              100 100              Barnyardgrass                                                                          100                                                                              50 100                                                                              95 100                                                                              50                                                                              95 50 80 40 95 50                                                                              80 100                                                                              40                                                                              70 90 100 100              Green Foxtail                                                                          95 70 100                                                                              80 100                                                                              80                                                                              100                                                                              40 80 40 95 90                                                                              40 95 40                                                                              95 70 --  --               Johnsongrass                                                                           100                                                                              40 70 70 90 50                                                                              95 30 70 30 60 80                                                                              90 80 30                                                                              30 60 90  100              __________________________________________________________________________             Compound No.                                                                  22 23 24 25 26 27 28 29 30 31 32 33 35 36 37 38 39 40                         Rate (kg/ha)                                                         Species  0.5                                                                              0.25                                                                             0.25                                                                             0.25                                                                             0.5                                                                              1.0                                                                              0.25                                                                             0.25                                                                             0.25                                                                             0.25                                                                             0.5                                                                              0.25                                                                             1.0                                                                              4.0                                                                              0.25                                                                              1.0                                                                             0.25                                                                             1.0               __________________________________________________________________________    Cotton   100                                                                              40 100                                                                              100                                                                              100                                                                              40 100                                                                              95 100                                                                              95 100                                                                              100                                                                              80 20 40 100                                                                              40 100               Soybean  50 40 90 95 95 60 95 95 100                                                                              100                                                                              100                                                                              100                                                                              60 10 40 100                                                                              40 90                Field Corn                                                                             70 20 90 95 80 70 80 80 90 100                                                                              100                                                                              100                                                                              100                                                                              10 70 100                                                                              10 100               Rice     90 0  80 95 50 20 40 40 90 95 100                                                                              100                                                                              80 10 30 100                                                                              20 100               Wheat    40 20 70 95 80 50 70 70 90 100                                                                              100                                                                              100                                                                              60 0  30 100                                                                              20 100               Field Bindweed                                                                         100                                                                              20 95 100                                                                              95 30 90 30 95 100                                                                              100                                                                              90 90 20 30 100                                                                              30 100               Morningglory                                                                           100                                                                              20 95 100                                                                              100                                                                              70 95 90 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0  80 100                                                                              90 100               Velvetleaf                                                                             100                                                                              30 100                                                                              100                                                                              100                                                                              20 100                                                                              70 100                                                                              100                                                                              100                                                                              100                                                                              90 0  100                                                                              100                                                                              60 100               Barnyardgrass                                                                          100                                                                              20 90 100                                                                              100                                                                              70 95 70 95 100                                                                              100                                                                              100                                                                              100                                                                              20 60 100                                                                              20 100               Green Foxtail                                                                          100                                                                              20 95 100                                                                              100                                                                              100                                                                              95 95 95 100                                                                              100                                                                              100                                                                              100                                                                              30 50 100                                                                              70 100               Johnsongrass                                                                           100                                                                              20 95 100                                                                              100                                                                              70 80 80 80 90 100                                                                              100                                                                              90 20 50 100                                                                              30 100               __________________________________________________________________________                                  Compound No.                                                                  41                                                                              42 43                                                                              44                                                                              45 46 47 48 49 93 94 96                                              Rate (kg/ha)                                                          Species 1.0                                                                             0.25                                                                             1.0                                                                             1.0                                                                             1.0                                                                              0.25                                                                             0.25                                                                             2.0                                                                              0.25                                                                             2.0                                                                              2.0                                                                              0.25              __________________________________________________________________________                          Cotton  40                                                                              95 95                                                                              40                                                                              90 100                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              100                                     Soybean 60                                                                              90 40                                                                              40                                                                              80 80 95 95 100                                                                              95 50 95                                      Field Corn                                                                            80                                                                              80 60                                                                              40                                                                              100                                                                              95 80 100                                                                              100                                                                              100                                                                              50 100                                     Rice    40                                                                              30 20                                                                              20                                                                              80 20 80 50 95 70 20 100                                     Wheat   50                                                                              40 10                                                                              40                                                                              80 60 90 50 100                                                                              95 40 100                                     Field Bindweed                                                                        30                                                                              40 0 50                                                                              95 100                                                                              100                                                                              100                                                                              100                                                                              -- -- --                                      Morningglory                                                                          50                                                                              60 90                                                                              50                                                                              95 100                                                                              100                                                                              100                                                                              100                                                                              80 40 100                                     Velvetleaf                                                                            30                                                                              100                                                                              40                                                                              40                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 85 100                                     Barnyardgrass                                                                         95                                                                              70 60                                                                              40                                                                              100                                                                              100                                                                              95 95 100                                                                              80 70 100                                     Green Foxtail                                                                         80                                                                              50 90                                                                              60                                                                              95 100                                                                              95 95 100                                                                              80 60 100                                     Johnsongrass                                                                          95                                                                              80 30                                                                              40                                                                              95 90 95 80 100                                                                              70 50 95                __________________________________________________________________________

I claim:
 1. An herbicidal compound of the general formula ##STR19## inwhich X is Br, Cl, F or haloalkyl;Y is Br, Cl, F, methyl, haloalkyl,nitro, or a radical of the formula R⁸ OCH₂ --, R⁸ SCH₂ --, R⁸ SOCH₂ --or R⁸ SO₂ CH₂ -- where R⁸ is C₁ -C₃ alkyl, C₂ -C₅ alkenyl, C₃ -C₅alkynyl, phenyl, or substituted phenyl; R³ is halogen, alkyl, haloalkyl,cyanoalkyl, arylalkyl, alkoxyalkyl, alkylthio, alkylsulfinyl,alkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl or alkylsulfonylalkyl;R² is alkyl, alkoxy, haloalkyl, alkenyl, alkynyl, cyanoalkyl,thiocyanoalkyl, or a group of the formula --alkylene--Y'-R⁵ in whichsaid alkylene group has 1 to 5 carbon atoms, Y' is oxygen or S(O)r inwhich r is 0 to 2, and R⁵ is alkyl, alkenyl or alkynyl; R is alkyl; R¹is hydrogen, a salt-forming group, alkyl, benzyl, haloalkyl, alkoxy, SO₂R, alkynyl, alkenyl, a group of the formula --alkylene--SO₂ R oralkoxymethyl or R and R₁ together is alkylene, said salt-forming groupbeing selected from Na, K, Ca, and ammonium.
 2. A compound as in claim 1in which X and Y are each halogen, R² is CHF₂, R³ is CH₃, R is loweralkyl and R¹ is hydrogen, a salt-forming group, lower alkyl or --SO₂ R.3. A compound as in claim 2 in which X is F, Cl or Br, Y is Cdl or Br, Ris lower alkyl and R¹ is H or a salt-forming group.
 4. A compound as inclaim 2 in which R is lower alkyl and R¹ is --SO₂ R.
 5. A compound as inclaim 2 in which R is lower alkyl and R¹ is lower alkyl.
 6. Anherbicidal composition comprising an herbicidally effective amount ofthe compound of claim 1 in admixture with a suitable carrier.
 7. Amethod for controlling undesired plant growth which comprises applyingto the locus where control is desired an herbicidally effective amountof the composition of claim
 6. 8. An herbicidal composition comprisingan herbicidally effective amount of the compound of claim 2 in admixturewith a suitable carrier.
 9. A method for controlling undesired plantgrowth which comprises applying to the locus where control is desired anherbicidally effective amount of the composition of claim
 8. 10. Anherbicidal composition comprising an herbicidally effective amount ofthe compound of claim 3 in admixture with a suitable carrier.
 11. Amethod for controlling undesired plant growth which comprises applyingto the locus where control is desired an herbicidally effective amountof the composition of claim
 10. 12. An herbicidal composition comprisingan herbicidally effective amount of the compound of claim 4 in admixturewith a suitable carrier.
 13. A method for controlling undesired plantgrowth which comprises applying to the locus where control is desired anherbicidally effective amount of the composition of claim
 12. 14. Anherbicidal composition comprising an herbicidally effective amount ofthe compound of claim 5 in admixture with a suitable carrier.
 15. Amethod for controlling undesired plant growth which comprises applyingto the locus where control is desired an herbicidally effective amountof the composition of claim
 14. 16. A compound as in claim 3 in which Ris methyl or ethyl.
 17. A compound as in claim 3 in which R is methyl.18. A method as in claim 11 including the steps of planting said locuswith soybeans and applying said composition pre-emergently to saidlocus.
 19. A compound as in claim 2 in which R is lower alkyl and R¹ ishydrogen or a salt-forming group.
 20. A compound as in claim 18 in whichR is methyl.
 21. A compound as in claim 19 in which X Y are each Cl. 22.An herbicidal composition comprising an herbicidally effective amount ofthe compound of claim 20 in admixture with a suitable carrier.
 23. Amethod for controlling undesired plant growth which comprises applyingto the locus where control is desired an herbicidally effective amountof the composition of claim 12.